US8329789B2 - Stabilizer composition for halogen-containing polymers - Google Patents

Stabilizer composition for halogen-containing polymers Download PDF

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US8329789B2
US8329789B2 US12/863,710 US86371009A US8329789B2 US 8329789 B2 US8329789 B2 US 8329789B2 US 86371009 A US86371009 A US 86371009A US 8329789 B2 US8329789 B2 US 8329789B2
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stabilizer composition
composition according
halogen
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titanium dioxide
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US20110143068A1 (en
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Bernhard Pelzl
Michael Schiller
Cornelia Damm
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Akdeniz Chemson Additives AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
    • B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article

Definitions

  • the present invention relates to a stabilizer composition for halogen-containing polymers, its use in the stabilization of halogen-containing polymers, in particular against undesired pinking, as well as mouldings, which contain this stabilizer composition.
  • Halogen-containing polymers and plastic materials, respectively, or mouldings prepared therefrom are inclined to substantial changes during their manufacturing method and due to the action of environmental influences.
  • this type of plastic materials may decompose or discolour under influence of heat and/or light.
  • various compounds or compositions have already been used.
  • a halogen-containing polymer such as for example polyvinyl chloride (PVC) changes into a polyene structure when a melt-forming process is carried out, whereby hydrochloric acid is eliminated and the polymer is colored.
  • PVC polyvinyl chloride
  • metal carboxylates as stabilizers into the resin, in order to improve the thermostability of the polymers.
  • metal burning during longer melt-forming processes, which imparts a blackening to the polymer
  • a number of combinations of inorganic and organic compounds are known to be stabilizers for halogen-containing polymers.
  • nitrogen-containing compounds as stabilizers came into the market. Nitrogen-containing stabilizer compounds have also been described in the patent literature.
  • DE 1 694 873 describes the use of uracils, which can stabilize against both heat and light.
  • EP 768 336 describes a stabilizer combination, which contains a pyrimidinone in addition to several components.
  • EP 736 569 describes the use of specific nitrogen compounds, which are characterised by a very good stabilizing effect for halogen-containing polymers both against oxidative, thermal and light-induced degradation. The color-stabilizing effect during thermal stress is particularly remarkable.
  • DE 1 954 273 describes the combination of titanium dioxide with a melamine as light-stabilizing pigment
  • DE 10 2004 037 369 describes a stabilizer system containing a linear or cyclic acylureide and/or a polyaminocrotonic acid ester and a polyepoxypropyl alcohol ether and/or a cyanamide derivative as well as a small amount of TiO 2 as pigment.
  • the object of the present invention is to provide new stabilizer compositions being particularly suitable for halogen-containing polymers, without having the above mentioned drawbacks of the known stabilizers.
  • the object of the invention is also to provide a universal titanium dioxide, which in combination with nitrogen-containing stabilizer compounds does not lead to pinking in sunlight or artificial light.
  • This object is solved according to the present invention by providing a stabilizer composition for halogen-containing polymers comprising titanium dioxide and at least one nitrogen-containing compound, wherein the titanium dioxide has an photo-electromotive force in ⁇ s-range > ⁇ 15 mV and an photo-electromotive force in the ms-range >+5 mV.
  • the stabilizer compositions according to the present invention provides an increased stability against the influence of sunlight and artificial light to halogen-containing polymers and the parts and products prepared therefrom.
  • pinking of the halogen-containing material can be prevented, if it is used in applications, which are used outdoors, such as for example in window profiles.
  • FIG. 2 illustrates a diagram for the determination and archiving of a color.
  • FIG. 3 illustrates a photo-EMK signal of a dispersion layer of the TiO 2 -charge Kronos 1001 with PVB as binder; about 2.7*10 13 quanta per flash; total absorption; flash distance 120 s.
  • FIG. 4 illustrates a photo-EMK signal of a dispersion layer of the TiO 2 -charge Kronos 1014 with PVB as binder; about 2.7*10 13 quanta per flash; total absorption; flash distance 120 s.
  • FIG. 5 illustrates a photo-EMK signal of a dispersion layer of the TiO 2 -charge Kronos 1071 with PVB as binder; about 2.7*10 13 quanta per flash; total absorption; flash distance 120 s.
  • FIG. 6 illustrates a photo-EMK signal of a dispersion layer of the TiO 2 -charge Kronos 1080 with PVB as binder; about 2.7*10 13 quanta per flash; total absorption; flash distance 120 s.
  • FIG. 7 illustrates a photo-EMK signal of a dispersion layer of the TiO 2 -charge prepared in accordance with the chloride process 2 with PVB as binder; about 2.7*10 13 quanta per flash; total absorption; flash distance 120 s.
  • FIG. 8 illustrates a photo-EMK signal of a dispersion layer of the TiO 2 -charge prepared in accordance with the chloride process 1 with PVB as binder; about 2.7*10 13 quanta per flash, total absorption; flash interval 120 s.
  • the stabilizer composition of the present invention may be used for halogen-containing polymers.
  • halogen-containing thermoplastic polymers are polyvinyl chloride (PVC), polyvinylidene chloride, chlorinated or chlorosulfonated polyethylene, chlorinated polypropylene or chlorinated ethylene/vinyl acetate copolymer or similar compounds.
  • Polymers of the PVC type are particularly favourable, i.e. vinyl chloride homopolymers and copolymers of vinyl chloride with other monomers.
  • Titanium dioxide essentially occurs in nature in three modifications: anatase, brookite and rutile.
  • Titanium dioxide has technical relevance as pigment in both anatase and rutile form.
  • the high refraction indices of 2.55 (anatase) and 2.75 (rutile) are responsible for the brightening and coverage ability and thus for the use as white pigment.
  • Rutile absorbs all light below 400 nm, i.e. the entire UV range, in case of a respective dosage.
  • the absorption of anatase is slightly shifted to shorter wavelengths.
  • brookite does not show any photo-catalytic activity.
  • the titanium dioxide used in the invention is titanium dioxide, which has a specific characteristic.
  • the TiO 2 has a photo-electromotive force in the ⁇ s-range > ⁇ 15 mV and a photo-electromotive force in the ms-range >+5 mV.
  • the titanium dioxide has a photo-electromotive force in the ⁇ s-range > ⁇ 10 mV and a photo-electromotive force in the ms-range >+10 mV.
  • photo-electromotive force denotes the effect, which occurs, if electrons from the valence band of a compound are transferred under the influence of light and/or heat into the next higher band, the so-called conduction band, wherein thereby a photo-semiconductor results.
  • the electron leaves a “hole”, into which an adjacent electron can jump.
  • electrons may jump from the conduction band back into the “hole” in the valence band.
  • This charge transfer of the photo-semiconductor can be characterized in form of the photo-EMK.
  • the photo-EMK also depends on the wavelength of the excitation flash. A photo-EMK can only be observed, if the sample is absorbing the excitation light. For example, TiO 2 only absorbs in the UV range.
  • the compounds, which should be examined, are introduced into a polymeric matrix, such as described in for example M. Schiller et al., Journal OF Photochemistry and Photobiology A: Chemistry, 149 (2002) 227-236.
  • a certain amount of the test substance for example 100 mg, was dispersed in a predetermined amount of polyvinyl butyral (PVB) in 1,2-dichloroethane, for example 3 g of a 10% solution, for example using ultrasound.
  • PVB polyvinyl butyral
  • 1,2-dichloroethane for example 3 g of a 10% solution, for example using ultrasound.
  • This mixture was poured onto a glass plate having an exactly defined surface.
  • the surface may be, for example about >27 cm 2 , for example about >47 cm 2 .
  • the applied layer should have been as thin as possible.
  • the optimum layer thickness results due to, for example, the mass of the PVBs. If more substance is weighed in the outlet surface has to be selected in larger scale. Drying of the layers is carried out in a solvent atmosphere. The dried dispersion layers are removed from the glass plate and the solvent residues are removed at room temperature under vacuum. The dispersion layers have a total absorption in the UV range and a layer thickness of, for example, about 60 to about 80 ⁇ m. The samples have been stored at a relative humidity of 100% (in the desiccator over water).
  • the sample is located between transparent front and back electrodes in an electrically insulated form ( FIG. 1 ).
  • a high-impedance voltmeter is connected to both electrodes.
  • a voltage and its decay process can be determined at the measurement device, by electroless tapping the voltage, which is developed in the sample, at the electrodes and which is recorded for example at an oscillograph.
  • the insulation between sample and electrodes is essential, as decay processes should be examined in the sample and thus electron transfer between sample and electrode needs to be avoided.
  • the transparent front electrode consists of quartz glass, which is vaporized with ITO, as this material is light-transmissive and exhibits corresponding electrical properties.
  • the back electrode may be for example brass, wherein other materials known to the skilled person may be used.
  • the light source may be a laser, for example a 100 kW nitrogen laser may be used.
  • the wavelength of the excitation flash depends on the used laser.
  • the wavelength of the excitation laser may be 337 nm.
  • the pulse duration is in the range from 0.2 to 0.5 ns, for example the pulse duration is 0.3 ns. It is advantageous that the maximum of the photo-EMK does not considerably depend on the intensity of the excitation flash.
  • ms range signal to 100 ms after the flash for registration of the slow decay processes.
  • the signal of the first flash is registered. Subsequently, an acquisition measurement may be carried out. In this case the sample is exposed several times in specific time intervals, for example in an interval of 120 s, wherein the oscillograph averages the signals. The acquisition measurement is performed in order to examine possible charge effects of the samples. Thus, the signal-to-noise ratio is improved increasing the accuracy of a kinetic analysis of the signals. After the acquisition measurement a new sample is inserted.
  • the measurements are carried out at normal pressure and at a temperature of 25° C. Different measurement conditions are also possible.
  • U max is a relative measure for the efficiency of separation of charge at exposure.
  • the decay process of the photo-EMK has been evaluated according to a bi-exponential time law (equation (1)).
  • U ( t ) U 1 0 exp( ⁇ k 1 t )+ U 2 0 exp( ⁇ k 2 t ) (1)
  • U 1 0 and U 2 0 represent charge carrier amounts at the beginning of the decay process near the surface (U 2 0 ) and in the volume (U 2 0 ), respectively.
  • the decay constants k 1 and k 2 are a relative measure for the speed of the recombination near the surface (k 1 ) and in the volume (k 2 ).
  • FIGS. 3 to 8 The photo-EMK signals of a dispersion layer of some of the tested TiO 2 -charges are shown in FIGS. 3 to 8 .
  • PVB was used as binder and a laser having 2.7*10 13 quanta per flash.
  • the flash interval was 120 s, the recorded time was between 0-2.5 ⁇ s and 0-200 ms, respectively.
  • the exact test procedure is described in the experimental section.
  • nitrogen compounds act as electron donors in stabilizer compositions.
  • DMAU 1,3-dimethyl-4-aminouracil
  • These nitrogen compounds may also act as electron donors in charge-transfer-(CT)-complexes.
  • Titanium dioxide may be considered as electron acceptor.
  • an electron is lifted from the valence band in the conduction band.
  • a positive charged hole remains, which may act as electron acceptor.
  • a CT-complex between titanium dioxides and DMAU may be formed.
  • combinations of PVC with a stabilizer composition of titanium dioxide and, for example, DMAU changes colour to pink after a certain amount of time in artificial light or natural light.
  • this pinking pink discoloration
  • the present invention is based on this principle, i.e. by using specific titanium dioxides this pinking may be eliminated.
  • the titanium dioxide according to invention may be added separately to the polymer or the polymer mixture. It is also possible to add the titanium dioxide together with the nitrogen compound or other (co)-stabilizers or the below listed additives to the polymer or a polymer mixture. For example a dosage in the extruder, e.g. in the vacuum zone, is also encompassed by the present invention.
  • the titanium dioxide according to the invention is preferably of rutile structure.
  • the inventive titanium dioxide may also be provided with a coating.
  • the coating may consist of inorganic or organic materials.
  • inorganic coatings may be based on aluminium oxides, silicium oxides and/or zirconium oxides.
  • organic coatings may be, for example, polydi-/monoalkyl siloxanes or stearic acid and their derivatives. The thickness of the coating is not important for the inventive use of the titanium dioxides.
  • the titanium dioxide should be present in fine distributed form and well dispersible.
  • the particle size is ⁇ 5 ⁇ m, for example ⁇ 2 ⁇ m. In another embodiment the particle size is ⁇ 1 ⁇ m. What is crucial is that the particle size is chosen in such a way that the stabilizing effect of the composition of the present invention occurs.
  • the uracil may have the following formula (I)
  • R 1 , R 2 , R 3 and R 4 are independently H, C 1 -C 18 alkyl, C 2 -C 5 alkenyl, C 1 -C 4 alkoxy, C 5 -C 8 cycloalkyl, C 5 -C 10 aryl, wherein R 3 and R 4 may be independently NHR 5 , wherein R 5 is independently to R 1 or R 2 , H, C 1 -C 18 alkyl, C 2 -C 6 alkenyl, C 1 -C 4 alkoxy, C 5 -C 8 cycloalkyl, C 5 -C 10 aryl.
  • alkyl refers to fully saturated aliphatic hydrocarbons.
  • an alkyl comprises 1 to 18 carbon atoms.
  • a numerical range, such as “1 to 18”, means, whenever it occurs, that for example an C 1 -C 18 alkyl group refers to an alkyl group comprising 1 carbon atom, 2 carbon atoms, 3 carbon atoms and so on, up to and including 20 carbon atoms.
  • the alkyl group may be optionally substituted.
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and the like.
  • alkenyl refers to aliphatic hydrocarbons having one or more double bonds.
  • an alkenyl comprises 2 to 6 carbon atoms.
  • the alkenyl group may be optionally substituted.
  • alkenyl compounds include, but are not limited to, ethenyl, propenyl, 1,4-butadienyl and the like.
  • alkoxy refers to aliphatic hydrocarbons having a —O-alkyl unit. In particular embodiments an alkoxy comprises 1 to 4 carbon atoms. The alkoxy group may be optional substituted. Examples of alkoxy compounds include, but are not limited to, methoxy, ethoxy, propoxy, tert.-butoxy and the like.
  • cycloalkyl refers to cyclic saturated hydrocarbons.
  • a cycloalkyl comprises 5 to 8 carbon atoms.
  • the cycloalkyl group may be optional substituted.
  • Examples of cycloalkyl compounds include, but are not limited to, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.
  • aryl refers to an aromatic ring wherein each of the atoms forming the ring is a carbon atom.
  • Aryl rings may be formed by five, six, seven, eight, nine, or more than nine carbon atoms.
  • aryl compounds may contain up to 15 carbon atoms.
  • the aryl group may be optionally substituted. Examples of aryl compounds include, but are not limited to, cyclopentadienyl, phenyl, and the like.
  • optional substituted refers to a group in which one or more hydrogen atoms have been replaced by a substituent.
  • the substituent may be alkyl, alkoxy, cycloalkyl, aryl, hetero aryl, OH, CN, halogen, NO 2 or an amine, however, is not limited to.
  • the uracil is 1,3-dimethyl-4-aminouracil.
  • R 1 , R 2 and R 3 may be as indicated above.
  • R 5 may be H, C 1 -C 18 alkyl, C 2 -C 6 alkenyl, C 1 -C 4 alkoxy, C 5 -C 8 cycloalkyl or C 5 -C 10 aryl, or wherein R 5 may be selected in such a way that a symmetrical aminocrotonic acid ester is formed.
  • Symmetrical in this context means that the molecule may be cleaved at a point, in order to obtain two similar molecules.
  • Examples for compounds from the group of ureas are urea and tetramethylurea.
  • the nitrogen compounds may be used in an amount of about 0.01 phr to about 1 phr or about 0.05 phr to about 0.8 phr. In one embodiment the nitrogen compounds may be used in an amount of about 0.1 to about 0.5 phr.
  • the titanium dioxide according to the invention may further be combined with one or more additives, such as for example primary stabilizers, co-stabilizers, zeolites, antioxidants, fillers, softeners, dyes, pigments, antistatic agents, surface-active agents, foaming agents, impact modifiers, UV stabilizers, lubricants, processing means or the like.
  • additives such as for example primary stabilizers, co-stabilizers, zeolites, antioxidants, fillers, softeners, dyes, pigments, antistatic agents, surface-active agents, foaming agents, impact modifiers, UV stabilizers, lubricants, processing means or the like.
  • Co-stabilizers are compounds providing additional stabilizing effect for halogen-containing polymers, if used in the stabilizer composition according to the present invention.
  • Possible co-stabilizers may be selected from the group consisting of 1,3-diketone compounds, polyols, metal salts, natural or synthetic minerals, such as hydrotalcites, hydrocalumites and zeolites, amino acid derivatives, organic esters of phosphorous acid, and epoxy compounds.
  • 1,3-diketone compounds include, but are not limited to, dibenzoylmethane, stearoyl benzoylmethane, palmitoyl benzoylmethane, myristoyl benzoylmethane, lauroyl benzoylmethane, benzoylacetone, acetylacetone, tribenzoylmethane, diacetylacetobenzol, p-methoxystearoyl acetophenone, acetoacetic acidester and acetylacetone as well as their metal salts, in particular those of lithium, sodium, potassium, calcium, magnesium, zinc, tin, titanium, aluminium and/or iron.
  • metal salts in particular those of lithium, sodium, potassium, calcium, magnesium, zinc, tin, titanium, aluminium and/or iron.
  • Co-stabilizers from the group of polyols include, but are not limited to, glycerol, pentaerythritol, di- and tripentaerythrit, trismethylolpropane (TMP), di-TMP, THEIC, sorbitol, mannitol, malitol, saccharides, disaccharides ⁇ in particular sucrose, 4-O- ⁇ -D galactopyranosyl-D-glucose, 4-O-alpha-D-glucopyranosyl-D-glucose, 6-O- ⁇ 6-deoxy-alpha-L-mannopyranosyl)-D-glucose, alpha-D-glucopyranosyl-alpha-D-glucopyranoside, 6-O-alpha-D-glucopyranosyl-D-glucose, 4-O- ⁇ -D-glucopyranosyl-D-glucose, 2-O- ⁇ -D-glucopyran
  • antioxidants include, but are not limited to, alkyl phenols, hydroxyphenylpropionates, hydroxybenzyl compounds, alkylidene bisphenoles, thiobisphenoles and aminophenoles, in particular, for example, 2,6-di-tert.-butyl-4-methyl-phenol, 2,6-di-benzyl-4-methyl-phenol, stearyl-3-(3′-5′-di-tert.-butyl-4′-hydroxyphenyl)propionate, 4,4′-thiobis-(3-methyl-6-tert.-butylphenol), 4-nonylphenol, 2,2′-methylenebis-(4-methyl-6-tert.-butylphenol), 2,5-di-tert.-butyl-hydroquinone, 4,4′,4′′-(1-methyl-1-propanyl-3-ylidene)tris-[2-(1,1-dimethylethyl)-5-methyl phenol, their neutral or
  • co-stabilizers from the group of metal salts include, but are not limited to, hydroxides, oxides, carbonates, basic carbonates and carboxylic acid salts of lithium, sodium, potassium, magnesium, calcium, aluminium, titanium and the like.
  • the metal salts may be salts of higher carboxylic acids, for example C 6 -C 22 carboxylic acids, such as for example stearic, palmitic, myristic, lauric, oleic, and ricinoleic acid.
  • Examples for natural and synthetic minerals include, but are not limited to, A3-, A4-, A5-zeolites, zeolites of the mordenite, erionite, faujasite X- or Y-type as well as ZSM-5-zeolites, hydrotalcites (of the Alcamizer-1 and -4 type) and/or mixtures thereof.
  • Preferred replaceable cations therein may be protons, ammonium-, lithium-, sodium-, potassium-, magnesium-, calcium-, zinc-, and/or tin-cations.
  • co-stabilizers from the group of amino acid derivatives include, but are not limited to, glycine, alanine, lysine, tryptophan, Acetylmethionine, pyrrolidone carboxylic acid, ⁇ -aminocrotonic acid, ⁇ -aminoacrylic acid, ⁇ -aminoadipic acid and the like, as well as the corresponding esters thereof.
  • the alcohol components of these esters may comprise monohydric alcohols, such as for example methyl alcohol, ethyl alcohol, propyl alcohol, i-propyl alcohol, butyl alcohol, ⁇ -ethylhexanol, octyl alcohol, i-octyl alcohol, lauryl alcohol, stearyl alcohol and the like, as well as polyols, such as for example ethylene glycol, propylene glycol, 1,3-butandiol, 1,4-butandiol, glycerol, diglycerol, trismethylolpropane, pentaerythritol, dipentaerythritol, erythrithol, sorbitol, mannitol and the like.
  • monohydric alcohols such as for example methyl alcohol, ethyl alcohol, propyl alcohol, i-propyl alcohol, butyl alcohol, ⁇ -ethylhexanol, octy
  • co-stabilizers from the group of esters of the phosphorous acid include, but are not limited to, triarylphosphites, such as for example triphenyl phosphite, tris(p-nonylphenyl) phosphite; alkylarylphosphite, such as for example monoalkyldiphenylphosphite, e.g.
  • diphenylisooctylphosphite diphenylisodecylphosphite
  • dialkylmonophenylphosphites such as for example phenyldiisooctylphosphite, phenyldiisodecylphosphite
  • trialkylphosphites such as triisooctylphosphite, tristearylphosphite and the like.
  • co-stabilizers from the group of epoxy compounds include, but are not limited to, various animal or vegetable oil, as for the example epoxy soy oil, epoxy rape oil, epoxidized carboxylic acid esters, such as for example epoxidized epoxy methyloleate, epoxy butyloleate, epoxidized alicyclic compounds, glycid ether, such as bisphenol-A-diglycidether bisphenol-A-diglycidether; glycidester, such as glycidyl acrylate, glycidyl methacrylate, their polymers and copolymers; and epoxidized polymers, such as epoxidized polybutadiene, epoxidized ABS, and the like.
  • glycid ether such as bisphenol-A-diglycidether bisphenol-A-diglycidether
  • glycidester such as glycidyl acrylate, glycidyl methacrylate, their polymers and copolymers
  • Exemplary, chalk or coated chalk should be mentioned as fillers, wherein the fillers are not limited thereon.
  • Paraffin wax may exemplary be used as a lubricant.
  • Fillers may be used in an amount of about 0 to about 100 phr or from about 1 to about 50 phr. In one embodiment of the present invention fillers may be used in an amount from about 2 to about 20 phr. Softeners may be used in an amount from about 0 to about 100 phr, for example from about 0.05 to about 50 phr. Lubricants may be used from about 0.05 to about 3 phr, for example from about 0.1 to about 2 phr.
  • halogen-containing polymers with the stabilizer composition according to the present invention the methods known in the state of the art may be used. Examples of such methods include, but are not limited to, calendering, extrusion, injection moulding, blow moulding and the like.
  • the stabilized halogen-containing polymers made according to the invention may be prepared from the stabilized halogen-containing polymers made according to the invention.
  • window profiles, pipes, floor coverings, roof sheets, cables and films may be prepared from the stabilized polymers.
  • the polymers may be used in materials for example for sport boats, rotor blades for wind-powered devices and in wagon building.
  • the a-value represents the color on the green-red axis.
  • Negative a-values show a green cast and positive a red cast. The higher the a-value, the stronger is the red cast. Therefore, as preferably neutral value for a in the present invention and a preferably slight change of this value, respectively, is desirably.
  • the present invention makes a remarkable and new contribution to the development of the state of the art, in particular for the processing and stabilization of PVC and other halogen-containing thermoplastic polymers.
  • the characterization of the titanium dioxides used in the above-mentioned examples by means of photo-EMK can be taken from Table 1 (kinetic parameters of the photo-EMK measurement in PVB (measurement range 0-2.5 ⁇ s, signals after that first laser flash).
  • the measurement of the photo-EMK is carried out as indicated in the above description.
  • 100 mg of the pigment have been dissolved in 3 g of a 10% polyvinyl butyral solution in 1,2-dichloroethane by means of ultrasound.
  • the mixture has been applied on a glass plate (27 cm 2 ).
  • After drying of the pigment the polymeric layer has been removed from the glass substrate.
  • the remaining solvent is removed in vacuum.
  • the voltage which is developing in the sample is tapped at the electrodes in an electroless way (as indicated above), i.e. measured without galvanic contact, as there are insulative films between the sample and the electrodes. This prevents charge injection from the electrodes into the sample.
  • the preamplifier has an impedance of about 1 T ⁇ and the photo-EMK measurement takes place without an external electric field. The maximum time resolution is about 40 ns. All experiments have been carried out under normal pressure and at 25° C. In all cases the signal of first laser flash has been recorded. In further test experiments the time difference between two flashes has been 120 s (acquisition measurement). A detailed description of the used photo-EMK apparatus can be found in G. Israel et al., J. Inform. Rec. 23 (1997), 559-584.
  • the maximum value of the photo-EMK is determined directly from the experimental curves, wherein the curves are kinetically evaluated according to a bi-exponential time, wherein the lifetime of the charge carriers near the surface and in the volume can be determined.
  • the results of the single measurements may also be taken from Tables 1 and 2 as well as FIGS. 3 to 8 .
  • the further characterization of the titanium dioxides used in the above-mentioned examples by means of photo-EMK can be taken from Table 2 (kinetic parameters of the photo-EMK measurement in PVB (measurement range 0-200 ms, signals after that first laser flash).
  • examples 2 and 7 which are not according to the invention, including the 1,3-dimethyl-4-aminouracil-containing formulations, the determined a-values show a significant positive, i.e. “red” shifting color change, after short, but intense irradiation time.
  • the a-value remains negative, i.e. green.
  • Inventive example 3, 4, 5 and 6, show a significant effect by the influence of the inventive stabilizer compounds.
  • the a-values are only slightly negative, i.e. at maximum a slight green cast may be observed.
  • pinking of the polymers and the products prepared therefrom, for example window profiles, can be prevented.
  • FIG. 9 contains the graphical illustration of the a-values (after 120 h in the Bandol Wheel) vs. the U max -values from Table 4 after taking out the initial color.

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DE102008005339A DE102008005339A1 (de) 2008-01-21 2008-01-21 Stabilisatorzusammensetzung für halogenhaltige Polymere
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CN111072574B (zh) * 2019-12-03 2023-03-14 广东工业大学 5,6-二氨基-1,3-二烃取代尿嘧啶及其制备方法
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CN112250907A (zh) * 2020-10-15 2021-01-22 广东宝利兴科技有限公司 一种新的缓释型pvc环保稳定剂
CN112226017A (zh) * 2020-10-15 2021-01-15 广东宝利兴科技有限公司 一种新的缓释型应用于pvc-uh管的环保稳定剂
CN113444287B (zh) * 2021-06-23 2022-04-08 浙江宏天新材料科技有限公司 一种改性水滑石及其制备方法、pvc热稳定剂及应用
CN114369067A (zh) * 2021-12-29 2022-04-19 广东科力新材料有限公司 一种酰胺基尿嘧啶及其制备方法与应用

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ES2424039T3 (es) 2013-09-26
US20110143068A1 (en) 2011-06-16
BRPI0907212A2 (pt) 2015-07-14
BRPI0907212B1 (pt) 2019-03-19
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AU2009207657B2 (en) 2013-10-03
EP2235099B1 (fr) 2013-05-22

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